CN103748156A - Acid resistant fluoroelastomer compositions - Google Patents

Acid resistant fluoroelastomer compositions Download PDF

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CN103748156A
CN103748156A CN201280040783.5A CN201280040783A CN103748156A CN 103748156 A CN103748156 A CN 103748156A CN 201280040783 A CN201280040783 A CN 201280040783A CN 103748156 A CN103748156 A CN 103748156A
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bismuth
fluoroelastomer
curable
acid
peroxide
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CN103748156B (en
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D.F.莱昂斯
P.A.莫肯
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Chemours Co FC LLC
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

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Abstract

Disclosed herein is a curable composition comprising a peroxide curable fluoroelastomer, an organic peroxide, a multifunctional coagent and an acid acceptor selected from the group consisting of carboxylic acid salts of bismuth and a bismuth oxycarboxylate. Cured articles made therefrom are resistant to volume swell in acids and in biodiesel fuel and said cured articles exhibit good heat resistance.

Description

Acidproof fluoroelastomer composition
Technical field
The present invention relates to curable fluoroelastomer composition, it comprises i) fluoroelastomer of peroxide-curable, ii) organo-peroxide, iii) multifunctional assistant, and iv) acid acceptor, described acid acceptor is selected from carboxylate salt and the oxycarboxylic acid bismuth of bismuth.
Background technology
There is excellent thermotolerance, oil-proofness and chemical-resistant fluoroelastomer and be widely used in sealing material, container and flexible pipe.The example of fluoroelastomer comprises and comprises vinylidene fluoride (VF 2) unit and at least one other can copolymerization fluorochemical monomer if R 1216 (HFP), tetrafluoroethylene (TFE), trifluorochloroethylene (CTFE), vinyl fluoride (VF) and fluorinated ethylene base ether are as perfluor (alkyl vinyl ether) multipolymer (PAVE).The object lesson of PAVE comprises perfluor (methylvinylether), perfluor (ethyl vinyl ether) and perfluor (propyl vinyl ether) (PPVE).Other fluoroelastomer comprises the multipolymer that comprises tetrafluoroethylene and perfluor (methylvinylether).
In order to manifest completely as the physical property of tensile strength, elongation and compressive set, elastomerics must be cured and vulcanizes or be cross-linked.With regard to fluoroelastomer, this generally realizes by following steps: uncured polymkeric substance (being fluoroelastomer gum) is mixed with polyfunctional solidifying agent, and heating gained mixture, thereby promote the chemical reaction of solidifying agent and reactive site along main polymer chain or side chain.The interchain that produced by these chemical reactions connects base and impels the forming of crosslinking polymer composition with three-dimensional net structure.The conventional solidifying agent for fluoroelastomer comprises the combination of organo-peroxide and multifunctional assistant.Conventionally for example metal oxide is joined in described composition, to improve the retentivity of elastomerics physical property (elongation and tensile strength) under high temperature (>200 ℃).
For example, yet curing fluoroelastomer goods can show unacceptable high volume swelling, 50-200 volume %; When sealing member is exposed to some chemical for a long time or at elevated temperatures as acid or biodiesel fuel, described high volume swelling degree can cause seal failure.Can swelling be minimized by remove metal oxide from described composition, but the elastomerics physical property under high temperature be impaired.Expectation has the fluoroelastomer of peroxide cure, and described fluoroelastomer has the combination of physical property maintenance under low volume swelling and high temperature in acid.
United States Patent (USP) 6,319,972B1 discloses and has comprised some bismuth carboxylate salt as thermoplastic vinylidene fluoride homopolymer and the multipolymer of thermo-stabilizer.
Summary of the invention
In one aspect, the invention provides curable fluoroelastomer composition, it comprises:
A) fluoroelastomer of peroxide-curable;
B) organo-peroxide;
C) multifunctional assistant; With
D) acid acceptor of every 100 weight part fluoroelastomer 1 to 60 weight parts, described acid acceptor is selected from carboxylate salt and the oxycarboxylic acid bismuth of bismuth.
Embodiment
The present invention relates to curable fluoroelastomer composition, it has the sour medium volume swelling of reduction when solidifying with organo-peroxide.Specifically, be exposed to nitric acid, due to the oxidation characteristic of described acid and due to the high-dissolvability of its salt in the aqueous solution, it has represented acid proof strict test.After being exposed to nitric acid, excessive swelling shows crosslinked fluoroelastomer network degraded.In addition, salpeter solution does not change between the shelf lives, and provide evaluate therein acid proof can reproducing medium.Curing fluoroelastomer composition has multiple end-use, comprises turbo-supercharger flexible pipe and the fuel management system with at least one viton goods that contact with biodiesel fuel.Due to biodiesel fuel comprise deliberately add or store or be exposed to the acidic components that produce by decomposition during water, so acid resistance is any elastomeric exclusive requirement contacting with biodiesel fuel.
So-called term " fuel management system " refer to for the manufacture of, store, transportation and supply, metering and control the equipment in biodiesel fuel.Fuel management system comprises those that for example, for example, comprise in biofuel manufactory, Motor vehicles (lorry, car, steamer), stationary diesel power set (generator, portable pumping plant), and to biodiesel fuel transportation, store and distribute relevant those.The concrete element of fuel management system includes but not limited to fuel container, pouring orifice flexible pipe, oil tank cover sealing part, burning line flexible pipe and tubing, valve, barrier film, fuel control sensor sealing member and fuel injector assembly, O shape ring, sealing member and packing ring.Any or all these elements all can comprise one or more viton goods that contact with biodiesel fuel.Curing viton goods include but not limited to fuel contact layer, valve packing, barrier film and the tank linning of sealing member, packing ring, O shape ring, tubing, multi-layer flexible pipe.
So-called " biodiesel fuel " refers to the fuel that is applicable to ignition (diesel oil) engine, and described engine is in harmonious proportion mutually with one or more biogenic (deriving from animal or plant) fatty acid alkyl ester (FAAE).These FAAE normally derive from fatty acid methyl ester or the ethyl ester of vegetables oil or Tallow, beef.Object lesson comprises rapeseed oil methyl ester (RME), soybean oil methyl esters (SME), palm-kernel oil methyl esters (PME) etc.Also comprise these materials based on FAAE and the blend of conventional oil base diesel oil fuel.Petrifaction diesel/biodiesel blend is called as Bxx fuel traditionally, and wherein " xx " is the volume percent of the biofuel based on FAAE in blend.For example, B100 represents the biodiesel fuel that does not comprise the petrochemical industry component of adding intentionally.B20 represents the biodiesel fuel that comprises 20 volume %B100 fuel and 80 volume % petroleum diesel fuel.
Being applicable to fluoroelastomer of the present invention is those that can be solidified by organo-peroxide and multifunctional assistant.
So-called " peroxide-curable " refers to and comprises along polymer chain, at chain end or simultaneously at the fluoroelastomer of these two locational Br or I cure site.
Along the cure site of fluoroelastomer chain normally due to the existence of the cure site monomer of the copolymerization that comprises bromine or iodine atom.The example of suitable cure site monomer includes but not limited to: i) brominated alkene; Ii) containing iodine alkene; Iii) brominated vinyl ether; And iv) containing iodoethylene base ether;
The cure site monomer of bromination can comprise other halogen, preferably fluorine.The example of brominated olefins cure site monomer is CF 2=CFOCF 2cF 2cF 2oCF 2cF 2br; Bromination trifluoro-ethylene; 4-is bromo-3,3,4,4-tetrafluoro butene-1 (BTFB); And other, bromine ethene for example, 1-is bromo-2,2-difluoroethylene; Hexafluoropropylene-based bromine; 4-is bromo-1,1, the fluoro-1-butylene of 2-tri-; 4-is bromo-1,1,3,3,4,4 ,-hexafluoro butylene; The bromo-3-of 4-is chloro-1,1,3,4,4-five fluorine butylene; 6-is bromo-5,5,6,6-tetrafluoro hexene; 4-bromine perfluor-1-butylene and 3,3-difluoro propenyl bromine.Ethylene bromide base ether cure site monomer for the present invention comprises the bromo-perfluoroethyl perfluorovinyl ether of 2-and CF 2br-R f-O-CF=CF 2(R ffor perfluorinated alkylidene) class fluorinated compound is as CF 2brCF 2o-CF=CF 2, and ROCF=CFBr or ROCBr=CF 2(wherein R is low alkyl group or fluoro-alkyl) class fluorinated ethylene base ether is as CH 3oCF=CFBr or CF 3cH 2oCF=CFBr.
Suitable iodate cure site monomer comprises the iodate alkene of following formula: CHR=CH-Z-CH 2cHR-I, wherein R be-H or-CH 3; Z is the straight chain that optionally comprises one or more ether oxygen atoms or the C of branching 1-C 18(entirely) fluorine alkylidene group, or as United States Patent (USP) 5,674, disclosed (entirely) fluorine polyoxyalkylene in 959.Other example of useful iodate cure site monomer is the unsaturated ethers of following formula: I (CH 2cF 2cF 2) noCF=CF 2and ICH 2cF 2o[CF (CF 3) CF 2o] ncF=CF 2deng, n=1-3 wherein, such as United States Patent (USP) 5,717, disclosed in 036.In addition, comprise that iodoethylene, 4-are iodo-3,3,4,4-tetrafluoro butene-1 (ITFB); 3-chlorine-4-iodine-3,4,4-trifluoro butylene; 2-is iodo-1,1,2,2-tetrafluoro-1-(vinyloxy group) ethane; The iodo-1-of 2-(perfluoro-ethylene oxygen base)-1,1 ,-2,2-tetrafluoroethylene; The iodo-1-of 1,1,2,3,3,3-hexafluoro-2-(perfluoro-ethylene oxygen base) propane; 2-iodine ethyl vinyl ether; 3,3,4,5,5,5-hexafluoro-4-iodine amylene; In interior suitable iodate cure site monomer, be disclosed in United States Patent (USP) 4,694 with iodine trifluoro-ethylene, in 045.The iodo-perfluoroethyl perfluorovinyl ether of allyl iodide and 2-is also useful cure site monomer.
Owing to using chain-transfer agent or molecular weight regulator during fluoroelastomer preparation, therefore containing iodine end group, brominated end group or their mixture, can optionally be present in the one or both ends of fluorine-containing elastomer polymer chain.When using, calculate chain-transfer agent amount so that the iodine content in fluoroelastomer or bromine content in 0.005-5 % by weight, preferably in the scope of 0.05-3 % by weight.
The example of chain-transfer agent comprises that it causes the iodine atomic linkage of bonding on the one or both ends of polymer molecule containing iodine compound.Methylene iodide; Isosorbide-5-Nitrae-diiodo perfluo-normal butane; Iodo-3,3,4 with 1,6-bis-, 4-tetrafluoro hexane is the representative of this type of reagent.The chain-transfer agent of other iodate comprises 1,3-diiodo perfluo propane; 1,6-diiodo perfluo hexane; The iodo-2-chlorine of 1,3-bis-perfluoropropane; 1,2-bis-(iodine difluoromethyl)-perfluorocyclobutane; One iodine R 116; One iodine perfluorinated butane; The iodo-1-hydrogen of 2-R 116 etc.Also comprise disclosed cyano group-iodine chain-transfer agent in European patent 0868447A1.Especially preferred is diiodinated chain transfer agents.
The example of brominated chain transfer agents comprises the bromo-2-iodine of 1-R 116; The bromo-3-iodine of 1-perfluoropropane; The iodo-2-of 1-is bromo-1, (such as the United States Patent (USP) 5,151,492 in disclosed) of 1-C2H4F2 C2H4F2 and other.
The object lesson that can be used for the fluoroelastomer in the present invention includes but not limited to comprise following multipolymer: i) vinylidene fluoride, R 1216 and optional tetrafluoroethylene, ii) vinylidene fluoride, perfluor (methylvinylether) and optional tetrafluoroethylene, iii) tetrafluoroethylene and perfluor (methylvinylether), and iv) tetrafluoroethylene and propylene.All rear a kind of polymkeric substance have iodine or bromine atoms along polymer chain, at two ends or along polymer chain with at two ends.
The organo-peroxide being applicable in the present composition includes but not limited to two (the tert-butyl peroxy bases)-3,5 of 1,1-, 5-trimethyl-cyclohexane; Two (tert-butyl peroxy base) hexanaphthenes of 1,1-; Two (tert-butyl peroxy base) octanes of 2,2-; Normal-butyl-4, two (tert-butyl peroxy base) valerates of 4-; Two (tert-butyl peroxy base) butane of 2,2-; 2,5-dimethylhexane-2,5-dihydroxyl superoxide; Ditertiary butyl peroxide; Tert-butyl peroxide isopropyl benzene; Dicumyl peroxide; α, α '-bis-(sec.-propyl between tert-butyl peroxy base) benzene; 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane; 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexene-3; Benzoyl peroxide, tert-butyl peroxy base benzene; 2,5-dimethyl-2,5-bis-(benzoyl peroxide)-hexane; Tert-butyl hydroperoxide toxilic acid; And tert-butyl hydroperoxide sec.-propyl carbonic acid.The preferred example of organo-peroxide comprises 2,5-dimethyl-2,5-bis-(tert-butyl peroxy base) hexane, dicumyl peroxide, and α, α '-bis-(sec.-propyl between tert-butyl peroxy base) benzene.Compounding amount is generally in the scope of every 100 weight part fluoroelastomer 0.05-5 weight parts, preferably in the scope of 0.1-3 weight part.Select this specified range, because if superoxide exists to be less than the amount of 0.05 weight part, vulcanization rate not and cause the poor demoulding.On the other hand, if superoxide exists to be greater than the amount of 5 weight parts, the compression set of cure polymer becomes and makes us unacceptable height.In addition, described organo-peroxide can be used singly or in a combination of two or more kinds.
Multifunctional assistant for curable compositions of the present invention is polyfunctional group unsaturated compound; for example triallyl cyanurate, isocyanuric acid trimethylammonium propylene, triallyl isocyanurate, isocyanuric acid trimethylammonium allyl ester, triacryl methylal (triacrylfonnal), trimellitic acid triallyl, N; N '-meta-phenylene bismaleimide, diallyl phthalate, tetraallyl poly P phenylene diamine terephthalamide, three (diallyl amine)-s-triazine, triallyl phosphite, diolefin and N, N-diallyl acrylamide.Compounding amount is generally in the scope of every 100 weight part fluoroelastomer 0.1-10 weight parts.Select this concrete concentration range, because if auxiliary agent exists to be less than the amount of 0.1 weight part, the cross-linking density of cure polymer makes us accepting.On the other hand, if auxiliary agent exists with the amount higher than 10 weight parts, it is gathered in surface during molding, causes poor stripping feature.Preferred auxiliary agent scope is 0.2-6 weight part/100 part fluoroelastomers.Described unsaturated compound can be used singly or in a combination of two or more kinds.
The curable composition of the present invention also comprises at least one acid acceptor of every 100 weight part fluoroelastomer 1 to 60 weight parts (preferably 4 to 40 parts), and described acid acceptor is selected from carboxylate salt and the oxycarboxylic acid bismuth of bismuth.Described bismuth compound reacts to be conducive to solidifying (being cross-linked) as acid acceptor, and as anionresin compound, to remove any acidic substance as HF or carboxylic acid.Know, bismuth salt has variable stoichiometry, and according to definite preparation and separation condition, the water of difference amount or hydroxide ion is incorporated in bismuth compound.When there is bismuthyl (BiO+) ionic structure, use " son " prefix in form.(Chemical?Reviews，1999，2601)。Suitable bismuth carboxylate compound comprises bismuth acetate, bismuth benzoate, Bismuth carbonate, bismuth citrate, 2 ethyl hexanoic acid bismuth, neodecanoic acid bismuth and Oxalic acid bismuth salt.Suitable oxycarboxylic acid bismuth compound comprises bismuth subgallate, bismuth subcarbonate and bismuth subsalicylate.
Except bismuth carboxylate or oxycarboxylic acid bismuth, in curable compositions of the present invention, also can there is other optional acid acceptor (for example zinc oxide, magnesium oxide, calcium hydroxide).If existed, the content of other acid acceptor is between 1 and 30 weight part/100 weight part fluoroelastomers.
Generally via Banbury mixer or rubber mill, fluoroelastomer, solidifying agent, acid acceptor and any other composition are incorporated in curable compositions.Then for example, by resulting composition sizing (molding or extrusion molding) and curing to form viton goods.Solidify and conventionally at approximately 150 ℃-200 ℃, carry out 1 to 60 minute.Can use conventional rubber vulcanizing machine, mould machine, forcing machine of being provided with suitable heating and solidification equipment etc.In addition, for best physical property and dimensional stability, preferably carry out after fixing operation, wherein in baking oven etc., molding or extrusion molding viton goods are being reheated to about 1-48 hour at approximately 180 ℃ of-275 ℃ of temperature conventionally.
example
testing method
By ASTM D471-96, the volume swelling degree (%) after soaking measure acidic medium on standard A STM D471 coupon in.Described coupon makes by solidifying viton plate, and under the condition described in example, is soaked in acidic medium.
Tensile properties is measured by ASTM D412.
Incompressible tension set performance is measured according to ASTM D395.
The present invention is by following instance but be not limited to following instance and further illustrate.
Fluoroelastomer FKM1 for described example is
Figure BDA0000468155650000061
gF-600S, the multipolymer of the vinylidene fluoride that comprises iodine cure site, R 1216 and the tetrafluoroethylene of 70 % by weight fluorine content, purchased from DuPont.
Fluoroelastomer FKM2 for described example is
Figure BDA0000468155650000062
gBL-600S, the multipolymer of the vinylidene fluoride that comprises iodine cure site, R 1216 and the tetrafluoroethylene of 68 % by weight fluorine content, purchased from DuPont.
Fluoroelastomer FKM3 for described example is
Figure BDA0000468155650000063
gF, the multipolymer of the vinylidene fluoride that comprises bromine cure site, R 1216 and the tetrafluoroethylene of 69.5 % by weight fluorine content, purchased from DuPont.
Fluoroelastomer FKM4 for described example is
Figure BDA0000468155650000072
gLT-600S, the multipolymer of the vinylidene fluoride that comprises iodine cure site, R 1216 and the perfluor (methylvinylether) of 64 % by weight fluorine content, purchased from DuPont.
For the fluoroelastomer FFKM1 of described example, be the tetrafluoroethylene that comprises iodine cure site and the multipolymer of perfluor (methylvinylether), and by partly in batch emulsion polymerization make.
All bismuth compounds for described example all derive from A1faAesar.
example 1 and Comparative examples A, B and C
By compounding composition in two roller mills, prepare the curable compositions of example 1 and Comparative examples A, B and C.Preparation is shown in Table I.
Described composite mold is moulded to slab, and at 177 ℃ cure under pressure 10 minutes.Then by curing slab after fixing 4 hours at 232 ℃.
The test block of being made by curing slab is exposed to 70% nitric acid 70 hours at 70 ℃.
This example shows, the composition exhibiting that comprises bismuth subsalicylate goes out sufficient acid resistance and acceptable thermotolerance.The composition exhibiting that comprises zinc oxide goes out sufficient thermotolerance but not good acid resistance.The composition exhibiting of containing metal oxide does not go out sufficient acid resistance but not good thermotolerance.
table I
Figure BDA0000468155650000071
1weight part/100 part rubber (being fluoroelastomer)
2triallyl isocyanurate auxiliary agent, purchased from DuPont
3organo-peroxide, purchased from R.T.Vanderbilt
example 2 and Comparative Example D, E and F
By compounding composition in two roller mills, prepare the curable compositions of example 2 and Comparative Example D, E and F.Preparation is shown in Table II.
Described composite mold is moulded to slab, and at 177 ℃ cure under pressure 10 minutes.Then by curing slab after fixing 4 hours at 232 ℃.
The coupon of being made by the piece solidifying is exposed to 70% nitric acid 70 hours at 70 ℃, and at 100 ℃, is exposed to 100% acetic acid 168 hours.
This example shows, based on 68 % by weight fluorine, is containing in the compound of weight polymers, and the viton that comprises bismuth subsalicylate illustrates than comprising zinc oxide or the better acid resistance of magnesian viton.
table II
Figure BDA0000468155650000081
4magnesium oxide, purchased from Martin Marietta Magnesium Specialties
example 3 and comparative example G, H and I
By compounding composition in two roller mills, prepare the curable compositions of example 3 and comparative example G, H and I.Preparation is shown in Table III.
Described composite mold is moulded to slab, and at 177 ℃ cure under pressure 10 minutes.Then by curing slab after fixing 4 hours at 232 ℃.
This example shows, bismuth subsalicylate can cause solidifying of brominated fluoroelastomer.The composition of containing metal oxide does not solidify.Also show, the performance of bismuth subsalicylate is different from bismuth oxide, and bismuth oxide does not cause solidifying of brominated fluoroelastomer yet.
table III
Figure BDA0000468155650000091
example 4 and 5 and Comparative Example J:
By compounding composition in two roller mills, prepare example 4 and 5 and the curable compositions of Comparative Example J.Preparation is shown in Table IV.
Described composite mold is moulded to slab and O shape ring (for compressive set test), and at 177 ℃ cure under pressure 10 minutes.Then make to solidify slab and O shape ring after fixing 4 hours at 232 ℃.
The test block of being made by curing slab is exposed to 70% nitric acid 70 hours at 70 ℃.
This example shows, the composition that comprises bismuth subsalicylate demonstrates sufficient acid resistance and acceptable thermotolerance in the fluoroelastomer that comprises perfluor (methylvinylether).Composition exhibiting without metal oxide goes out sufficient acid resistance but not good thermotolerance.
table IV
example 6
By compounding composition in two roller mills, prepare the curable compositions of example 6.Preparation is shown in Table V.
Described composite mold is moulded to slab and O shape ring (for compressive set test), and at 165 ℃ cure under pressure 10 minutes.Then make to solidify slab and O shape ring after fixing 4 hours at 232 ℃.
The test block of being made by curing slab is exposed to 70% nitric acid 70 hours at 70 ℃.
This example shows, the composition that comprises bismuth subsalicylate demonstrates sufficient acid resistance and acceptable thermotolerance in Perfluoroelastomer.
table V
Figure BDA0000468155650000111
example 7-9
By compounding composition in two roller mills, prepare the curable compositions of example 7,8 and 9.Preparation is shown in Table VI.
Described composite mold is moulded to slab, and at 177 ℃ cure under pressure 10 minutes.Then by curing slab after fixing 4 hours at 232 ℃.
The test block of being made by curing slab is exposed to 70% nitric acid 70 hours at 70 ℃.
These examples show, the carboxylate salt of bismuth is improving fluoroelastomer composition acid resistance, and it is also effective keeping abundant thermotolerance aspect simultaneously.
table VI
Composition, phr 1 Example 7 Example 8 Example 9
FKM1 100 100 100
Bismuth subsalicylate 5 0 0
Bismuth citrate 0 5 0
Bismuth subcarbonate 0 0 5
Carbon black N990 30 30 30
Diak7 2 3 3 3
Varox?DBPH-50 3 15 1.5 1.5
Former tensile properties ? ? ?
T B，MPa 18.6 18.6 19.9
E B，％ 309 282 325
The variation per-cent of the tensile properties at 250 ℃ after 70 hours ? ? ?
T B +1 -3 -9
E B +16 +23 +5
The variation per-cent of the tensile properties at 250 ℃ after 168 hours ? ? ?
T B -24 -28 -32
E B +32 +37 +12
Volume swelling degree ? ? ?
At 70 ℃, be exposed to 70% nitric acid 70 hours 12 14 15

Claims (10)

1. curable fluoroelastomer composition, comprises:
A) fluoroelastomer of peroxide-curable;
B) organo-peroxide;
C) multifunctional assistant; With
D) acid acceptor of every 100 weight part fluoroelastomer 1 to 60 weight parts, described acid acceptor is selected from carboxylate salt and the oxycarboxylic acid bismuth of bismuth.
2. curable fluoroelastomer composition according to claim 1, wherein said acid acceptor is the carboxylate salt of bismuth, and the carboxylate salt of described bismuth is selected from bismuth acetate, bismuth benzoate, Bismuth carbonate, bismuth citrate, 2 ethyl hexanoic acid bismuth, neodecanoic acid bismuth and Oxalic acid bismuth salt.
3. curable fluoroelastomer composition according to claim 1, wherein said acid acceptor is oxycarboxylic acid bismuth, described oxycarboxylic acid bismuth is selected from bismuth subgallate, bismuth subcarbonate and bismuth subsalicylate.
4. curable fluoroelastomer composition according to claim 3, wherein said acid acceptor is bismuth subcarbonate.
5. curable fluoroelastomer composition according to claim 3, wherein said acid acceptor is bismuth subsalicylate.
6. curable fluoroelastomer composition according to claim 1, the copolymerization units that the fluoroelastomer of wherein said peroxide-curable comprises vinylidene fluoride, R 1216 and tetrafluoroethylene.
7. curable fluoroelastomer composition according to claim 1, the copolymerization units that the fluoroelastomer of wherein said peroxide-curable comprises vinylidene fluoride, perfluor (methylvinylether) and tetrafluoroethylene.
8. curable fluoroelastomer composition according to claim 1, the copolymerization units that the fluoroelastomer of wherein said peroxide-curable comprises tetrafluoroethylene and perfluor (methylvinylether).
9. curing fluoroelastomer goods, it is made by composition claimed in claim 1.
10. fuel management system, comprises curing fluoroelastomer goods claimed in claim 9.
CN201280040783.5A 2011-08-31 2012-06-26 Acidproof fluoroelastomer composition Expired - Fee Related CN103748156B (en)

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JP6109173B2 (en) 2017-04-05
US20130053519A1 (en) 2013-02-28

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